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EP2256236A1 - Verfahren zur Herstellung von leitenden Verbundfasern mit einem hohen Anteil an Nanoröhren - Google Patents

Verfahren zur Herstellung von leitenden Verbundfasern mit einem hohen Anteil an Nanoröhren Download PDF

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Publication number
EP2256236A1
EP2256236A1 EP10163360A EP10163360A EP2256236A1 EP 2256236 A1 EP2256236 A1 EP 2256236A1 EP 10163360 A EP10163360 A EP 10163360A EP 10163360 A EP10163360 A EP 10163360A EP 2256236 A1 EP2256236 A1 EP 2256236A1
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EP
European Patent Office
Prior art keywords
nanotubes
conductive composite
fibers
fiber
manufacturing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10163360A
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English (en)
French (fr)
Inventor
Patrice Gaillard
Philippe Poulin
Célia Mercadier
Maryse Maugey
Sandy Moisan
Alain Derre
Cécile ZAKRI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Arkema France SA
Original Assignee
Centre National de la Recherche Scientifique CNRS
Arkema France SA
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Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS, Arkema France SA filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP2256236A1 publication Critical patent/EP2256236A1/de
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals

Definitions

  • the present invention relates to a process for obtaining conductive composite fibers based on homo- or copolymer of vinyl alcohol with a high content of nanotubes capable of providing thermal and / or electrical conduction, in particular of carbon nanotubes. It also relates to the conductive composite fibers obtainable by this method, as well as their uses.
  • Carbon nanotubes are known and possess particular crystalline structures, tubular, hollow and closed, composed of atoms arranged regularly in pentagons, hexagons and / or heptagons, obtained from carbon.
  • CNTs generally consist of one or more graphite sheets wound coaxially.
  • SWNTs single wall nanotubes
  • Multi Wall Nanotubes or MWNTs Multi Wall Nanotubes
  • CNTs have many powerful properties, namely electrical, thermal, chemical and mechanical.
  • composite materials intended in particular for the automotive, nautical and aeronautical industries, electromechanical actuators, cables, resistant wires, chemical detectors, energy storage and conversion, electron emission displays, electronic components, and functional textiles.
  • conductive such as NTCs allow the heat and electrical dissipation of heat and electric charges arising during friction.
  • the CNTs when synthesized, are in the form of a disorganized powder, consisting of entangled filaments, which makes them difficult to implement in order to exploit their properties. In particular, to exploit their mechanical and / or electrical properties on a macroscopic scale, it is necessary for the CNTs to be present in large quantities and oriented in a preferred direction.
  • Another approach for producing CNT-loaded polymer fibers is to mix the nanotubes and a polymer in the same solution before spinning.
  • the solution thus produced is then injected into a static bath or in a flow which induces the coagulation of the polymer.
  • the nanotubes mixed with the polymer are trapped in the structure and the final object is a composite fiber loaded with carbon nanotubes.
  • the advantage of this principle is that it relies on the coagulation of the polymer and not directly on the coagulation of the nanotubes. Coagulation of the polymer allows consolidated fibers to be obtained more rapidly which can be easily handled and extracted from the coagulation baths to be, for example, washed, dried, drawn and wound.
  • the spinning of polymer fibers by solvent coagulation and their treatments are well described in the literature.
  • the fibers described by Zhang et al. contain a mass fraction of not more than 3% of carbon nanotubes.
  • process according to the invention may optionally comprise other preliminary, intermediate and / or subsequent stages to those mentioned above, provided that these do not adversely affect the formation of the conductive composite fiber. .
  • fiber is meant, within the meaning of the present invention, a strand whose diameter is between 100 nm (nanometers) and 300 microns (micrometers), preferably between 1 and 100 microns (micrometers), better, between 2 and 50 ⁇ m (micrometers).
  • This structure may also be porous or non-porous.
  • a fiber is intended to ensure the holding of a mechanical part and does not constitute a tube or pipe for the transport of a fluid.
  • the nanotubes consist of at least one chemical element chosen from the elements of columns IIIa, IVa and Va of the periodic table.
  • the nanotubes must be capable of providing thermal and / or electrical conduction; they can thus be based on boron, carbon, nitrogen, phosphorus or silicon.
  • they may be constituted or contain carbon, carbon nitride, nitride of boron, boron carbide, boron phosphide, phosphorus nitride or carbon boronitride, or silicon.
  • carbon nanotubes are used. These are graphitic carbon fibrils, hollow, each having one or more graphitic tubular walls oriented along the axis of the fibril.
  • the nanotubes usually have a mean diameter ranging from 0.1 to 100 nm (nanometers), more preferably from 0.4 to 50 nm (nanometers) and better still from 1 to 30 nm (nanometers) and advantageously a length of 0, 1 to 10 ⁇ m (micrometers).
  • Their length / diameter ratio is preferably greater than 10 and most often greater than 100 or even greater than 1000.
  • Their specific surface area is, for example, between 100 and 500 m 2 / g (including limits), generally between 100 and 300 m 2.
  • the multiwall nanotubes may for example comprise from 5 to 15 sheets (or walls) and more preferably from 7 to 10 sheets. These nanotubes can be treated or not.
  • Carbon nanotubes are commercially available or can be prepared by known methods.
  • An example of crude carbon nanotubes is especially commercially available from the company Arkema France under the trade name Graphistrength® ® C100.
  • Hyperion Catalysis International Inc. describes the synthesis of carbon nanotubes. More particularly, the process comprises contacting a metal-based particle such as, in particular, iron, cobalt or nickel, with a gaseous compound based on carbon, at a temperature of between 850 ° C. and 1200 ° C. C, the dry weight proportion of the carbon-based compound relative to the metal-based particle being at least about 100: 1.
  • a metal-based particle such as, in particular, iron, cobalt or nickel
  • nanotubes may be, optionally and optionally in combination, purified, treated (for example oxidized) and / or milled before being used in the process according to the invention.
  • the grinding of the nanotubes may in particular be carried out cold or hot and be carried out according to the known techniques used in devices such as ball mills, hammers, grinders, knives, jet gas or any other system grinding capable of reducing the size of the entangled network of nanotubes. It is preferred that this grinding step is performed according to a gas jet grinding technique and in particular in an air jet mill, or in a ball mill.
  • the purification of the crude or milled nanotubes can be carried out by washing with a sulfuric acid solution, so as to rid them of any residual mineral and metallic impurities originating from their preparation process.
  • the weight ratio of the nanotubes to the sulfuric acid may especially be between 1: 2 and 1: 3 (limits included).
  • the purification operation may also be carried out at a temperature ranging from 90 to 120 ° C, for example for a period of 5 to 10 hours. This operation may advantageously be followed by rinsing steps with water and drying the purified nanotubes.
  • the purification may also consist of a heat treatment at high temperature, typically greater than 1000 ° C.
  • the oxidation of the nanotubes is advantageously carried out by putting them in contact with a solution of sodium hypochlorite containing from 0.5 to 15% by weight of NaOCl and preferably from 1 to 10% by weight of NaOCl, for example in a weight ratio of nanotubes to sodium hypochlorite ranging from 1: 0.1 to 1: 1.
  • the oxidation is advantageously carried out at a temperature below 60 ° C. and preferably at room temperature, for a duration ranging from a few minutes to 24 hours. This oxidation operation may advantageously be followed by filtration and / or centrifugation, washing and drying steps of the oxidized nanotubes.
  • the nanotubes In order to eliminate the catalyst metal residues, it is also possible to subject the nanotubes to a heat treatment of at least 1000 ° C., for example 1200 ° C.
  • the first step of the process according to the invention consists in forming a dispersion of nanotubes in a solution of homo- or copolymer of vinyl alcohol, in the presence of at least one stabilizing agent covalently or non-covalently bonded to the nanotubes.
  • the homo- or copolymer of vinyl alcohol is the polyvinyl alcohol itself.
  • its molecular weight may be between 5,000 and 300,000 g / mol. Its degree of hydrolysis may be greater than 96%, or even greater than 99%.
  • the term "stabilizing agent” is intended to mean a compound that allows homogeneous dispersion of the nanotubes in the solution, which protects the nanotubes from coagulation in the presence of the homo- or copolymer of vinyl alcohol, but which does not interfere with the coagulation of the homo- or copolymer of vinyl alcohol in a coagulation solution.
  • the stabilizing agent (s) according to the invention are bonded to the nanotubes either covalently or non-covalently.
  • the stabilizing agent is non-covalently bonded to the nanotubes, it may be chosen from essentially nonionic surfactants.
  • the term "essentially nonionic surfactant” is intended to mean a nonionic amphiphilic compound, cited for example in McCutcheon's 2008 "Emulsifiers and Detergents", and preferably having an HLB (hydrophilic-lipophilic balance). from 13 to 16, as well as block copolymers containing hydrophilic blocks and lipophilic blocks and having a low ionicity, for example 0% to 10% by weight of ionic monomer and 90% to 100% of nonionic monomer.
  • HLB hydrophilic-lipophilic balance
  • the stabilizing agent is covalently bonded to the nanotubes
  • it is preferably a hydrophilic group, preferably a polyethylene glycol group grafted onto the nanotubes.
  • the grafting of reactive units such as polyethylene glycol groups on the surface of the nanotubes can be carried out according to any method known to those skilled in the art.
  • the person skilled in the art may relate to the publication of B. Zhao et al. (Synthesis and Characterization of Water Soluble Single-Walled Carbon Nanotube Graft Copolymers, J. Am Chem Soc. (2005) Vol 127 No 22 ).
  • the nanotubes are dispersed in dimethylformamide (DMF) and are contacted with oxalyl chloride.
  • DMF dimethylformamide
  • PEG polyethylene glycol
  • the nanotubes thus grafted are purified.
  • the dispersion produced in the first step of the process according to the invention comprises a solvent which is preferably chosen from water, dimethylsulfoxide (DMSO), glycerol, ethylene glycol, diethylene glycol and triethylene glycol. , diethylene triamine, ethylene diamine, phenol, dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone and mixtures thereof.
  • a solvent which is preferably chosen from water, dimethylsulfoxide (DMSO), glycerol, ethylene glycol, diethylene glycol and triethylene glycol. , diethylene triamine, ethylene diamine, phenol, dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone and mixtures thereof.
  • the solvent is chosen from water, DMSO and mixtures thereof in all proportions.
  • the pH of the aqueous dispersion can be maintained preferably between 3 and 5 by addition of one or more acids, which can be chosen from inorganic acids, such as sulfuric acid, nitric acid and hydrochloric acid, organic acids such as acetic acid, tartaric acid and oxalic acid and mixtures of organic acid and organic acid salt such as acid citric acid and sodium citrate, acetic acid and sodium acetate, tartaric acid and potassium tartrate, tartaric acid and sodium citrate.
  • inorganic acids such as sulfuric acid, nitric acid and hydrochloric acid
  • organic acids such as acetic acid, tartaric acid and oxalic acid and mixtures of organic acid and organic acid salt such as acid citric acid and sodium citrate, acetic acid and sodium acetate, tartaric acid and potassium tartrate, tartaric acid and sodium citrate.
  • the dispersion may comprise boric acid, borate salts, or mixtures thereof.
  • the dispersion may also comprise a salt selected from zinc chloride, sodium thiocyanate, calcium chloride, aluminum chloride, lithium chloride, rhodanates and mixtures thereof. They make it possible to optimize the rheological properties of the dispersion and to promote the formation of the fiber.
  • the dispersion is carried out by means of ultrasound or a rotor-stator system or a ball mill. It can be carried out at room temperature, or by heating, for example, between 40 and 120 ° C.
  • the dispersion thus produced during the first step of the process according to the invention may comprise from 2% to 30% by weight of homo- or copolymers of vinyl alcohol, from 0.1% to 5% of nanotubes, from 0.1% to 5% of stabilizing agent, relative to the total mass of the dispersion, including the solvent.
  • the second step of the process consists in injecting said dispersion obtained during the first step into a coagulation solution to form a pre-fiber, in the form of monofilament or multi-filaments.
  • coagulation solution means a solution which causes the homo- or copolymer of vinyl alcohol to solidify.
  • the coagulation solution comprises a solvent chosen from water, an alcohol, a polyol, a ketone and their mixtures, more preferably a solvent chosen from water, methanol, ethanol, butanol, propanol, isopropanol, glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene and mixtures thereof, and even more preferably a solvent selected from water, methanol, ethanol, a glycol acetone and their mixtures.
  • a solvent chosen from water, an alcohol, a polyol, a ketone and their mixtures more preferably a solvent chosen from water, methanol, ethanol, butanol, propanol, isopropanol, glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene and mixtures thereof, and even more preferably a solvent
  • the coagulation solution advantageously has a temperature of between 10 and 80 ° C. If the solvent of the coagulation solution is essentially organic, such as methanol, the coagulation solution advantageously has a temperature between -30 and 10 ° C.
  • the coagulation solution may comprise one or more salts intended to promote the coagulation of the homo- or copolymer of vinyl alcohol, chosen from alkaline salts or desiccant salts such as ammonium sulphate, sulphate of potassium, sodium sulfate, sodium carbonate, sodium hydroxide, potassium hydroxide and mixtures thereof.
  • alkaline salts or desiccant salts such as ammonium sulphate, sulphate of potassium, sodium sulfate, sodium carbonate, sodium hydroxide, potassium hydroxide and mixtures thereof.
  • the coagulation solution may comprise one or more additional compounds which are intended to improve the mechanical properties, the water resistance of the fiber and / or facilitate the spinning of the fiber.
  • the coagulation solution may therefore comprise at least one compound selected from boric acid, borate salts and mixtures thereof.
  • the coagulation solution is saturated with salts.
  • the dispersion is injected during the second step of the process according to the invention through one or a set of needles and / or one or a set of nonporous cylindrical or conical nozzles into the coagulation solution, which can be static (static bath) or in motion (flow).
  • the average injection speed of the dispersion may be between 0.1 m / min and 50 m / min, preferably between 0.5 m / min and 20 m / min.
  • the coagulant solution induces coagulation in the form of a pre-fiber by solidification of the homo- or copolymer of vinyl alcohol.
  • the nanotubes are trapped in the polymer that solidifies.
  • the next step of the process according to the invention consists in extracting, continuously or not, the pre-fiber from the coagulation solution.
  • the wash tank preferably includes water.
  • the washing step can eliminate a portion of the peripheral polymer of the pre-fiber and thus enrich (up to 70% by weight) the composition of the pre-fiber into nanotubes.
  • the washing bath may comprise agents which make it possible to modify the composition of the pre-fiber or which chemically interact with it.
  • chemical or physical crosslinking agents in particular borate salts or dialdehydes, may be added to the bath to reinforce the pre-fiber.
  • the washing step can also make it possible to eliminate the agents, in particular the surfactants, potentially detrimental to the mechanical or electrical properties of the fiber.
  • a drying step is also included in the process according to the invention. This step can take place either directly after extraction or after washing. In particular, if it is desired to obtain a polymer-enriched fiber, it is desirable to dry the pre-fiber directly after the extraction.
  • the drying is preferably carried out in an oven that will dry the pre-fiber through a gas flowing in an interior duct of the oven. The drying can also be carried out by infrared radiation.
  • the method according to the invention may also comprise a winding step, and optionally a hot stretching step performed between the drying step and the winding step. It may also include stretching in solvents at different times.
  • This stretching step may be carried out at a temperature above the glass transition temperature (Tg) of the homo- or copolymer of vinyl alcohol and preferably below its melting point (if it exists).
  • Tg glass transition temperature
  • Such a step, described in the patent US 6,331,265 enables the nanotubes and the polymer to be oriented substantially in the same direction, along the axis of the fiber, and thus to improve the mechanical properties of the latter, in particular its Young's modulus and its rupture threshold.
  • the draw ratio defined as the ratio of the length of the fiber after drawing to its length before drawing, may be between 1 and 20, preferably between 1 and 10, included. Stretching can be done in one go, or several times, allowing the fiber to relax slightly between each stretch.
  • This stretching step is preferably conducted by passing the fibers through a series of rolls having different rotational speeds, those which unroll the fiber rotating at a lower speed than those receiving it.
  • the fibers may be passed through ovens arranged between the rolls, or heated rollers may be used, or these two techniques may be combined. This stretching step makes it possible to consolidate the fiber and to achieve high breaking point stresses.
  • Another subject of the present invention is the conductive composite fibers that can be obtained according to the method of the invention.
  • Said conductive composite fibers obtained are characterized in that they contain from 5 to 70% by weight of nanotubes, preferably from 5 to 50%, more preferably from 5 to 30%, and more preferably from 5 to 25%, by in relation to the total weight of the fibers. It is therefore possible to obtain composite fibers with a high content of nanotubes.
  • the conductive composite fibers obtained according to this process have a resistivity which can be between 10 -3 and 10 5 ohm.cm at room temperature. This electrical conductivity can be further improved by heat treatments.
  • the manufacture of these composite parts can be carried out according to various processes, generally involving a step of impregnating the composite fibers.
  • conductive according to the invention by a polymeric composition containing at least one thermoplastic material, elastomeric or thermosetting.
  • This impregnation step may itself be carried out according to various techniques, depending in particular on the physical form of the polymeric composition used (pulverulent or more or less liquid).
  • the impregnation of the conductive composite fibers is preferably carried out according to a fluidized bed impregnation process, in which the polymeric composition is in the form of powder. Pre-impregnated fibers are thus obtained.
  • preimpregnated fiber fabrics of identical or different composition, can be stacked to form a plate or a laminated material, or alternatively subjected to a thermoforming process.
  • the pre-impregnated fibers may be combined to form ribbons which may be used in a filament winding process which makes it possible to obtain hollow pieces of almost unlimited shape, by winding the ribbons on a mandrel having the shape of the part to be made.
  • the manufacture of the finished part comprises a step of consolidating the polymeric composition, which is for example melted locally to create zones for fixing the fibers pre-impregnated with each other and / or to secure the fiber ribbons pre-impregnated with each other. impregnated in the filament winding process.
  • a film from the polymeric impregnating composition in particular by means of an extrusion or calendering process, said film having for example a thickness of about 100 ⁇ m, then of placing it between two conductive composite fiber mats according to the invention, the assembly then being hot pressed to allow the impregnation of the fibers and the manufacture of the composite part.
  • the present invention thus has for another object composite materials comprising conductive composite fibers according to the invention, bonded together by weaving or by a polymeric composition.
  • the dispersion was then injected into a static bath of a saturated sodium sulfate coagulant solution (320 g / L) at 40 ° C.
  • the pre-fiber was extracted from the coagulation bath after a residence time of less than ten seconds. It was then dried by infra-red radiation, then redirected into a washing bath containing water. After 1 min, it was dried again by infrared radiation and then wound.
  • the final fiber obtained contains 8% of nanotubes in mass. This value was obtained by thermogravimetric analysis (TGA).
  • TGA thermogravimetric analysis
  • the fiber is cylindrical and homogeneous and has been mechanically characterized by traction. It has a breaking energy of 475 J / g, an elongation at break of 425% stretching and a Young's modulus of 3 GPa. After hot stretching at 200 ° C of 400%, its Young's modulus increases to 29 GPa and its rupture threshold increases to 12% stretching.
  • Composite fibers were made starting from aqueous dispersions of multiwall nanotubes. 0.9% by weight of nanotubes and 1.2% Brij®78 were dispersed in water. By the same method as described in Example 1, fibers loaded with 17% multiwall nanotubes were obtained.
  • These fibers have the advantage of combining good mechanical properties with quite interesting electrical properties, since they are electrically conductive, with a resistivity of 10 ⁇ .cm. They have a toughness of 340 MPa, a Young's modulus of 5.5 GPa and an elongation at break of 240%.
  • the solution was then injected into a static bath of a saturated sodium sulfate coagulant solution (320 g / L) at 40 ° C to form a fiber.
  • the final fiber obtained contains 12% of nanotubes in mass. It has a toughness of 360 MPa, a Young's modulus of 4 GPa and an elongation at break of 325%, as well as a resistivity of 30 ⁇ .cm.
  • Example 3 The dispersion described in Example 3 was injected into a coagulant bath containing sodium hydroxide (50 g / L) and sodium sulfate (300 g / L) at 40 ° C.
  • the final fiber obtained contains 12% of nanotubes in mass. It has a toughness of 320 MPa, a Young's modulus of 7 GPa and an elongation at break of 200%, as well as a resistivity of 100 ⁇ .cm.
  • the dispersion was then injected into a methanol coagulant bath at -20 ° C containing 10% DMSO to form 8% nanotube filled fibers.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Inorganic Fibers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
EP10163360A 2009-05-27 2010-05-20 Verfahren zur Herstellung von leitenden Verbundfasern mit einem hohen Anteil an Nanoröhren Withdrawn EP2256236A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR0953508A FR2946177B1 (fr) 2009-05-27 2009-05-27 Procede de fabrication de fibres composites conductrices a haute teneur en nanotubes.

Publications (1)

Publication Number Publication Date
EP2256236A1 true EP2256236A1 (de) 2010-12-01

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EP10163360A Withdrawn EP2256236A1 (de) 2009-05-27 2010-05-20 Verfahren zur Herstellung von leitenden Verbundfasern mit einem hohen Anteil an Nanoröhren

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Country Link
US (1) US20110017957A1 (de)
EP (1) EP2256236A1 (de)
JP (1) JP2010281024A (de)
CN (1) CN101899723A (de)
FR (1) FR2946177B1 (de)
TW (1) TW201111569A (de)
WO (1) WO2010136704A1 (de)

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WO2013011250A1 (fr) * 2011-07-21 2013-01-24 Arkema France Fibres composites conductrices a base de graphene
FR2983850A1 (fr) * 2011-12-09 2013-06-14 Commissariat Energie Atomique Procede de fabrication de fibres crues et cuites a base de ceramique(s)
CN105297239A (zh) * 2015-09-17 2016-02-03 无锡市长安曙光手套厂 一种释香织物及其制备方法
CN109502570A (zh) * 2018-12-14 2019-03-22 郑州大学 导电的大应变碳纳米管复合薄膜、制备方法及测试方法

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FR3007412B1 (fr) 2013-06-20 2015-07-17 Centre Nat Rech Scient Procede de recuperation de fibres organiques a partir d'un materiau composite
FR3019563B1 (fr) * 2014-04-03 2016-04-29 Centre Nat Rech Scient Procede de preparation de fibres macroscopiques de dioxyde de titane par extrusion unidirectionnelle continue, fibres obtenues et applications
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CN104940989A (zh) * 2015-06-24 2015-09-30 苏州乔纳森新材料科技有限公司 一种可吸收缝合线及其制备方法
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CN109502570A (zh) * 2018-12-14 2019-03-22 郑州大学 导电的大应变碳纳米管复合薄膜、制备方法及测试方法

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FR2946177A1 (fr) 2010-12-03
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